Conductivity percolation transition of Agx(Ge0.25Se0.75)100−x glasses

The ionic conductivity of several chalcogenide glasses increases abruptly with mobile ion addition from values typical of insulating materials (10⁻¹⁶–10⁻¹⁴ Ω⁻¹ cm⁻¹) to values of fast ionic conductors (10⁻⁷–10⁻¹ Ω⁻¹ cm⁻¹). This change is produced in a limited concentration range pointing to a percolation process. In a previous work [M. Kawasaki, J. Kawamura, Y. Nakamura, M. Aniya, Solid State Ionics 123 (1999) 259] the transition from semiconductor to fast ionic conductor of Ag_x(Ge_0.25Se_0.75)_100−x glasses was detected at x¹ ≅ 10 at.% in the form of a steep change in the conductivity. Ag_x(Ge_0.25Se_0.75)_100−x glasses with x ⩽ 25 at.%, prepared by a melt quenching method, are investigated by impedance spectroscopy in the frequency range 5 Hz–2 MHz at different temperatures, T, from room temperature to 363 K and by DC measurements at room temperature. The conductivity of the glasses, σ, was obtained as a function of silver concentration and temperature. For x ⩾ 10 at.% our results are in agreement with those reported by Kawasaki et al. [M. Kawasaki, J. Kawamura, Y. Nakamura, M. Aniya, Solid State Ionics 123 (1999) 259]. The percolation transition was observed in the range 7 ⩽ x ⩽ 8. The temperature dependence of the ionic conductivity follows an Arrhenius type equation σ = (σ_o/T) · exp(−E_σ/kT). The activation energy of the ionic conductivity, E_σ, and the pre-exponential term, σ_o, are calculated. The results are discussed in connection with other chalcogenide and chalcohalide systems and linked with the glass structures.     

Thermal and optical properties of CuO–BaO–B2O3–P2O5 glasses

CuO-doped barium borophosphate glasses in a series of xCuO–(45 − x)BaO–10B₂O₃–45P₂O₅ in molar ratio with x = 0–15 mol% were prepared by a melt-quenching technique. All the glasses had excellent thermal stability against crystallization. Glass transition temperature, thermal expansion coefficient and molar volume decrease with increasing CuO concentration. The linear relationship between the absorption coefficient and CuO concentration exists for a peak wavelength in the transitions of ²A_1g → ²B_1g, ²B_2g → ²B_1g, ²E_g → ²B_1g. The relationship between the properties and glass structure evaluated by Raman spectroscopy is discussed.     

Effect of silver doping on the electrical properties of a-Sb2Se3

This paper reports the effect of Ag-doping on electrical properties of a-Sb₂Se₃ in the temperature range 230–340 K and frequency range 5–100 kHz. The variation of transport properties with thermal doping has been studied. Ag-doping produces two homogeneous phases in the sample, which are found to be voltage dependent in the temperature range studied and frequency dependent in lower frequency region (0.1–10 kHz). Activation energy E_g and C′ [= σ₀ exp (γ/k), where γ, is the temperature coefficient of the band gap] calculated from dc conductivity has been found to vary from (0.42 ± 0.01) eV to (0.26 ± 0.01) eV and (4.11 ± 0.01) × 10⁻⁵ to (2.90 ± 0.02) × 10⁻⁶ Ω⁻¹ cm⁻¹ respectively. Ag-doping can be used to make the sample useful in device applications.     

Vapor growth and characterization of pyrite (FeS2) doped with Co,Ni, and As: Variations in semiconducting properties

Pyrite (FeS₂) crystals doped with As, Ni and Co were synthesized with chemical vapor transport over an 18 cm horizontal gradient of 700–600 °C in evacuated quartz tubes, from a mixture of FeS and S, with FeBr₃ as a transport agent. Sulfur fugacity and thus S:Fe stoichiometry was constrained by the Fe_1−xS/FeS_2−y buffer. As, Ni and Co concentrations were ∼3–800 ppm, ∼200–1500 ppm and ∼ 450–3700 ppm, respectively.Semiconducting properties were measured at room temperature using a van der Pauw and Hall measurement system. Ni and Co-doped pyrite are n-type while As-doped pyrite tends to be p-type. Resistivity for Co-doped pyrite ranged from 0.009 to 0.02 Ω cm while for Ni- and As-doped pyrite, resistivity ranged from 2 to 17 Ω cm. Undoped pyrite resistivity ranged from 15 to 85 Ω cm. Carrier concentration was similar for undoped and Ni-doped pyrite, ranging from 10¹⁵ to 10^16.6 cm⁻³, while for Co-doped pyrite it ranged from 10^18.7 to 10^19.3 cm⁻³ and for As-doped pyrite it ranged from 10¹⁴ to 10¹⁸ cm⁻³. Hall mobility was similar for Co and Ni-doped pyrite ranging from 60 to 270 cm² v⁻¹ s⁻¹ while for undoped pyrite it ranged from 8 to 70 cm² v⁻¹ s⁻¹. Hall mobility for As-doped pyrite ranged from 55.0 to 0.2 cm² v⁻¹ s⁻¹ for electrons and from 0.1 to 11.3 cm² v⁻¹ s⁻¹ for holes with the exception of one sample (of 22). These values should be viewed more as trends than as definitive. The results obtained for Ni, Co, and undoped pyrite are similar to those reported in the literature while results for As-doped synthetic pyrite have not previously been reported.     

Properties and structure of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glass systems

(1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses were studied for the progressive percentage substitution of Na₂O for Li₂O at the constant mole of Al₂O₃ and SiO₂. The crystallization temperature at the exothermic peak increased from 898 to 939 °C when the Na₂O content increases from 0 to 0.6 mol. The coefficient of thermal expansion and density of these as-quenched glasses increase from 6.54 × 10⁻⁶ °C⁻¹ to 10.1 × 10⁻⁶ °C⁻¹ and 2.378 g cm⁻³ to 2.533 g cm⁻³ when the Na₂O content increases from 0 to 0.4 mol, respectively. The electrical resistivity has a maximum value at Na₂O · (Li₂O + Na₂O)⁻¹ = 0.4. The activation energy of crystallization decreases from 444 to 284 kJ mol⁻¹ when the Na₂O content increased from 0 to 0.4 mol. Moreover, the activation energy increases from 284 kJ mol⁻¹ to 446 kJ mol⁻¹ when the Na₂O content increased from 0.4 to 0.6 mol. The FT-IR spectra show that the symmetric stretching mode of the SiO₄ tetrahedra (1035–1054 cm⁻¹) and AlO₄ octahedra (713–763 cm⁻¹) exhibiting that the network structure is built by SiO₄ tetrahedra and AlO₄.     

Dilithium dialuminium trisilicate phase obtained using coal bottom ash

The Li₂Al₂Si₃O₁₀ glass-ceramics well crystallized and with a regular morphology was produced starting from a mixture of Li₂CO₃, TiO₂, Al₂O₃ and coal bottom ash, after reducing the magnetite phase content. Its measured thermal expansion coefficient in the temperatures range from 25 °C to 300 °C is α_(25–300) = −23.4 × 10⁻⁷ °C⁻¹. This value is ≈18% smaller than that for the commercial lithium glass-ceramics (−23.4 × 10⁻⁷ °C⁻¹ to 50 × 10⁻⁷ °C⁻¹).     

Initiation and propagation of shear bands in Zr-based bulk metallic glass under quasi-static and dynamic shear loadings

The effect of strain rate on the initiation and propagation of shear bands in the Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass under shear loading was investigated. The quasi-static (at a strain rate of 1.5 × 10⁻³ s⁻¹) and the dynamic shear tests (at a strain rate of 1.4 × 10³ s⁻¹) were conducted at room temperature using a GATAN Microtest-2000 instrument and a split Hopkinson pressure bar (SHPB) with a specially designed ‘Plate-shear’ specimen, respectively. The complete process of shear band initiation, propagation, and shear band unstable propagation-induced fracture was revealed. The experimental results demonstrated that the macroscopic shear strength is relatively insensitive to the strain rate, whereas shear band initiation and fracture are significantly dependent on strain rate. A dimensionless Deborah number was introduced to characterize the effect of the strain rate on the formation of shear bands. Additionally, the observed numerous liquid droplets and melted belts on the fracture surface at high-strain rates demonstrate that the adiabatic heating exerts a significant effect on fracture behavior of the material.     

Magnetic and magnetoelastic properties of cobalt–iron amorphous–nanocrystalline pulsed laser deposited thin films

We prepared pulsed laser deposited planar and cylindrical amorphous–nanocrystalline Co–Fe thin films using the corresponding target with composition Co_1−xFe_x, x = 0, 0.02, …, 1.0. Their room temperature spontaneous magnetization, M_s (film), was always a fraction of the M_s of the corresponding crystalline alloy, M_s (film) = γ M_s (crystal): γ ≈ 0.8 for pure Co, γ ≈ 0.88 for the Co₃₅Fe₆₅ film and γ ≈ 0.94 for pure Fe. Their isotropic magnetostriction coefficient, λ_s, was also determined. From pure Co to 30 at.% Fe λ_s values were similar to those corresponding to the crystalline alloys: from pure Co to 4 at.% Fe was negative and of the order of 10⁻⁶; λ_s increased to 10⁻⁵ up to 25 at.% Fe and achieved 10⁻⁴ from 30 at.% Fe to 90 at.% Fe; λ_s decreased to 10⁻⁵ for pure Fe. A chemical short-range order between the Co atoms surrounded by the Fe ones, increasing the magnetic moment of Fe atoms, was used to explain the observed behavior.     

Deformation behaviors of a tungsten-wire/bulk metallic glass matrix composite in a wide strain rate range

Using melt infiltration casting a composite (W-BMG) of Zr_41.25Ti_13.75Ni₁₀Cu_12.5Be_22.5 bulk metallic glass reinforced with tungsten wires has been produced and its quasi-static and dynamic deformations are investigated within the strain rates ranging from 1 × 10⁻⁴ to 2 × 10³ s⁻¹. The lengthwise frozen-in stress of the composite during the fabrication process is also calculated. The quasi-static stress–strain behavior is discussed in detail in light of the observation of the appearances of the specimens. The study reveals that the strain rate sensitivity exponent of 0.022 of the W-BMG composite is half that of the monolithic tungsten, which is a result of the frozen-in stress.     

Molecular dynamics in glass-forming poly(phenyl methyl siloxane) as investigated by broadband thermal,dielectric and neutron spectroscopy

The molecular dynamics of glass-forming poly(methyl phenyl siloxane) (PMPS) is studied by thermal (10⁻³–5 × 10² Hz), dielectric (10⁻³–10⁹ Hz) and neutron (5 × 10⁸–10¹² Hz) spectroscopy. Because of the broad frequency range of 15 orders of magnitude the study provides a precise determination of glassy dynamics in a wide temperature range using different probes. The relaxation rates extracted from the different methods agree quantitatively in both their absolute values and in their temperature dependencies. A detailed analysis of the temperature dependence of the relaxation rate f_p by a derivative technique shows that the α-relaxation of PMPS has to be characterized by a high and a low temperature branch separated by a crossover temperature T_B = 250 K. In both temperature ranges the temperature dependence of f_p has to be described by Vogel/Fulcher/Tammann laws with different Vogel temperatures. Also the analysis of the dielectric strength in its temperature dependence gives a crossover behavior from a low to a high temperature region with a similar value of T_B. T_B can be interpreted as onset of cooperative fluctuations and the formation of dynamical heterogeneities. The dependence of the relaxation rate on the scattering vector Q extracted from neutron scattering obeys a power law τ ∼ Q^−Slope, where the power Slope varies between Slope = 2 and Slope = 3.5 with increasing temperature. This anomalous dependence of the relaxation time on the momentum transfer is discussed in terms of dynamic heterogeneities in the underlying motional processes even at temperatures above T_B. Besides the segmental dynamics the fast Methyl group rotation is considered as well. The relaxation rates of this process have an activated temperature dependence with an activation energy of 8.3 kJ/mol. The data were discussed in the framework of the threefold jump model were the incoherent elastic scattering from ‘fixed’ atoms which are frozen on the time scale of the Methyl group rotation was taken into account.     

Protein–solvent and weak protein–protein interactions in halophilic malate dehydrogenase

With the aim to correlate the solvation, stability and solubility properties of halophilic malate dehydrogenase, we characterized its weak interparticle interactions by small-angle neutron scattering in various solvents. The protein concentration dependence of the apparent radius of gyration and forward scattered intensity extrapolated from Guinier plots, and thus the second virial coefficient, A₂, were determined for each solvent condition. In NaCl 1M+2-methylpentane-2,4-diol 30%, a solvent that promotes protein crystallization, A₂ is negative, −0.4×10⁻⁴ ml mol g⁻² and indicating attractive interactions; in ammonium sulfate 3M, in which the protein precipitates at high concentrations, A₂∼0. In 2–5M NaCl, 1–3.5M NaOAc, 1–4.5M KF or 1–2M (NH₄)₂SO₄, in which the protein is very soluble, A₂ is positive with a value of the order of 0.4×10⁻⁴ ml mol g⁻² which decreases with increasing salt concentration. In MgCl₂ however, A₂ increases with increasing salt concentration from 0.2 to 1.3M.     

Structure of amorphous NaCl–glucose system studied by X-ray diffraction and IR methods

X-ray diffraction and diffuse reflection IR spectroscopic measurements have been carried out on amorphous NaCl–glucose mixtures, a-(NaCl)_x(glucose)_1−x, with x = 0, 0.05, 0.1 and 0.15, in order to obtain structural information on the intermolecular hydrogen-bonded interaction between glucose molecules affected by the presence of NaCl. The difference distribution function Δg^inter(r) was derived from the Fourier transform of the difference intermolecular interference term Δi^inter(Q) between X-ray intermolecular interference terms observed from amorphous NaCl-glucose and pure glucose samples. A negative peak appears at r ≈ 2.5 Å in the Δg^inter(r) observed for the 10 mol% NaCl sample, while, the Δg^inter(r) for the 15 mol% NaCl sample does not show pronounced negative peak. On the other hand, the IR spectra for the O–H stretching region (2300 ⩽ ν ⩽ 3800 cm⁻¹) indicate that hydrogen bonds between glucose molecules are significantly collapsed in the samples containing 5–15 mol% NaCl. These results imply that the contribution from the Na⁺⋯Cl⁻ contact ion pair is dominated in the 15 mol% NaCl sample.     

Optical properties and infrared-to-visible upconversion in Er3+-doped GeO2–Bi2O3 and GeO2–PbO–Bi2O3 glasses

Luminescence properties and upconversion studies of germanate glasses in ternary GeO₂–PbO–Bi₂O₃ and binary GeO₂–Bi₂O₃ systems containing Er₂O₃ (0.1–1.0 wt%) are presented for the first time. The Judd-Ofelt parameters found for these glasses are: Ω₂ = 4.50 × 10⁻²⁰ cm², Ω₄ = 1.55 × 10⁻²⁰ cm² and Ω₆ = 0.69 × 10⁻²⁰ cm² for binary glasses and Ω₂ = 4.44 × 10⁻²⁰ cm², Ω₄ = 1.82 × 10⁻²⁰ cm² and Ω₆ = 0.39 × 10⁻²⁰ cm² for ternary glasses. The refractive index of these glasses is found to be ∼2. The transition ⁴I_13/2 → ⁴I_15/2 is peaked at ∼1.53 μm and shows a radiative lifetime around 5 ms. Both systems exhibit similar emission cross-section at 1.53 μm around 0.8 × 10⁻²⁰ cm². Upconverted green emission at ∼530 nm (²H_11/2 → ⁴I_15/2) and ∼550 nm (⁴S_3/2 → ⁴I_15/2) and red emission at ∼668 nm (⁴F_9/2 → ⁴I_15/2) are observed under 980 nm cw excitation. Our results suggest that these glasses are promising candidates for applications in photonics.     

Influence of hydrogen on the thermomechanical properties of a-CNx:H and a-CNx films deposited by glow discharge and ion beam assisted deposition

The coefficient of thermal expansion (CTE), Young’s modulus, Poisson’s ratio, stress and hardness of a-CN_x and a-CN_x:H were investigated as a function of nitrogen concentration. Hydrogenated films were prepared by glow discharge, GD, and unhydrogenated films were prepared by ion beam assisted deposition, IBAD. Using nanohardness measurements and the thermally induced bending technique, it was possible to extract separately, Young’s modulus and Poisson’s ratio. A strong influence of hydrogen, in a-CN_x:H films, was observed on the CTE, which reaches about ∼9 × 10⁻⁶ C⁻¹, close to that of graphite (∼8 × 10⁻⁶ C⁻¹) for nitrogen concentration as low as 5 at.%. On the other hand, the CTE of unhydrogenated films increases with nitrogen concentration at a much lower rate, reaching 5.5 × 10⁻⁶ C⁻¹ for 33 at.% nitrogen.     

Thermal lens study of PbO–Bi2O3–Ga2O3–BaO glasses doped with Yb3+

The aim of this paper is to present a study of the thermal lens technique in quantifying the thermo optical coefficients: ds/dT (optical path change with temperature), thermal diffusivity and conductivity of PbO–Bi₂O₃–Ga₂O₃–BaO glasses doped with Yb³⁺. The thermal lens results indicate that the heat generation, as a function of the incident wavelength, resembles the absorption band ²F_7/2 → ²F_5/2 of Yb³⁺. Thermal diffusivity of 2 × 10⁻³ cm²/s and thermal conductivity of 4.5 × 10⁻³ W/K cm were obtained and are similar to other glasses already reported in previous literature. The results emphasize that the thermal lens technique can be a powerful tool to study the heat generation of new glassy systems.     

Properties of sodium-based ternary phosphate glasses produced from readily available phosphate salts

Three series of phosphate glasses were produced by melting together sodium phosphate salt (NaH₂PO₄) and the phosphate salts of either calcium (CaHPO₄), magnesium (MgHPO₄ · 3H₂O) or iron (FePO₄ · 2H₂O) in a 5% gold/95% platinum crucible at 1200 °C. The glass compositions were confirmed by EDX and XRD analysis. Glass transition temperature (T_g), density and durability in water were determined for all the compositions. Maximum metal oxide contents before devitrification were between 55% and 59% for CaO + Na₂O and 59% and 62% for MgO + Na₂O. The normalized equivalent for Fe₂O₃ + Na₂O was between 55% and 61%. Density values for the glasses lay between 2.49 and 2.75 g cm⁻³. T_gs lay between 295 °C and 470 °C. Degradation rates in deionized water at 37 °C lay between 0.03 g cm⁻² h⁻¹ for Na phosphate glasses and 9 × 10⁻⁶ g cm⁻² h⁻¹ for Ca phosphate glasses, 3 × 10⁻⁶ g cm⁻² h⁻¹ for Mg phosphate glasses and <3 × 10⁻⁶ g cm⁻² h⁻¹ for Fe phosphate glasses. The effect of metal addition on properties goes as Fe > Mg > Ca for degradation rates and T_g and Fe > Mg ≈ Ca for density. The change in properties with metal addition was seen to be linear for Fe and Ca additions but not with Mg addition. This is in agreement with the anomalous behavior of magnesium phosphate glasses.     

Preparation of mixed arsenic/antimony chalcogenide glasses and some optical and thermo-physical properties

The preparation of mixed glasses of As₂S_3−xSe_x (x = 0–3) and (1 − y) · As₂S₃y · Sb₂S₃ (y = 0–1) has been carried out by an in situ pouring technique. X-ray diffraction (XRD) was used to confirm the glassy nature of the materials and monitor devitrification. Visible-IR transmission, photoluminescence, refractive index and micro-Raman were measured as a function of composition. Microhardness (MH) and thermal expansion coefficient (TEC) were also measured. Raman peaks in As₂S₃ and As₂Se₃ were observed around 338 cm⁻¹ and 230 cm⁻¹, respectively in this first composition series in which S was replaced by Se. When As was replaced by Sb, in the case of second composition series, the As₂S₃ related Raman peak became broader and shifted to lower wave number, reflecting some structural change/devitrification. MH increased (1.31–1.50 GPa) with Se and Sb content while the TEC was found to decrease (2.5–1.4 × 10⁻⁵/K). The progressive increase in the content of either Se or Sb in As₂S₃ is anticipated to modify bond lengths and bond angles. The combined effect of these structural modifications would change the local structure of the glass forming a more rigid glass network thereby increasing the hardness and decreasing TEC.     

Diffusion coefficient of K+ in ion exchanged glasses calculated from the refractive index and the Vickers hardness profiles

The top faces of float glass samples were exposed to vapors resulting from the decomposition of KNO₃ at 565 °C for up to 32 h. X-ray dispersive spectra (EDS) show that K⁺ ions migrate into the glass. The K⁺ concentration profile was obtained and its diffusion coefficient was calculated by the Boltzmann–Matano technique. The mean diffusion coefficient was approximately 10 × 10⁻¹¹ cm² s⁻¹. It was observed that the refractive index and the Vickers hardness decrease with the depth (after the removal of successive layers), and their profiles were thus obtained. These profiles enabled the calculation of the diffusion coefficient of K⁺ through the Boltzmann–Matano technique, with mean results ranging between 6 × 10⁻¹¹ and 30 × 10⁻¹¹ cm² s⁻¹.     

Sol–gel derived organic–inorganic hybrid electrolytes for thin film electrochromic devices

Sol–gel derived, lithium ion conducting organic–inorganic hybrid electrolytes for ambient temperatures applications, have been synthesized from tetraethyl orthosilicate (TEOS), poly(ethylene oxide) (PEO), propylene carbonate (PC), propylene oxide, butyl acrylate, butyl methacrylate, ethyl acetoacetate and LiClO₄ precursors. Mass fractions of the organic additions in the gels were of ca 30 mass% for gels 0/B, F–H and 40 mass% for gel J. The colorless transparent or translucent hybrid materials obtained in this work were aged at room temperature for at least three weeks and then dried at 80 °C for 3 h. The morphology and structure of all compositions were investigated by scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX), Fourier transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance. Amorphous nature of the hybrids was confirmed by X-ray diffraction. SEM, FTIR and NMR analysis showed structural properties and [SiO₄] tetrahedrons poly-condensation process to be strongly influenced by organic additives have been employed. Room temperature ionic conductivities of the hybrid electrolytes were in a range of 9.84 × 10⁻⁴–1.56 × 10⁻³ Ω⁻¹ cm⁻¹.     

Erbium activated HfO2 based glass–ceramics waveguides for photonics

(100 − x)SiO₂ − xHfO₂ (x = 10, 20, 30 mol) glass–ceramics planar waveguides activated by 0.3 mol% Er³⁺ ions were prepared by sol–gel route, using dip-coating deposition on v-SiO₂ substrates. High resolution transmission electron microscopy has shown that after an adapted heat treatment, the resulting materials show nanocrystalline structures. The glass–ceramics waveguides were characterized by m-line, Raman, losses measurements, and photoluminescence spectroscopy. Photoluminescence spectroscopy has demonstrated the embedding of erbium ions in the nanocrystals. The results are discussed with the aim of assessing the role of hafnia on the structural, optical and spectroscopic properties of erbium doped silica hafnia glass–ceramics planar waveguides.